WO2000022688A9 - Enzymatic battery - Google Patents

Enzymatic battery

Info

Publication number
WO2000022688A9
WO2000022688A9 PCT/US1999/018804 US9918804W WO0022688A9 WO 2000022688 A9 WO2000022688 A9 WO 2000022688A9 US 9918804 W US9918804 W US 9918804W WO 0022688 A9 WO0022688 A9 WO 0022688A9
Authority
WO
Grant status
Application
Patent type
Prior art keywords
compartment
electrode
battery
enzyme
electron
Prior art date
Application number
PCT/US1999/018804
Other languages
French (fr)
Other versions
WO2000022688A3 (en )
WO2000022688A2 (en )
Inventor
Michael J Liberatore
Leszek Hozer
Attiganal N Sreeram
Rajan Kumar
Chetna Bindra
Zhonghui H Fan
Original Assignee
Sarnoff Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M14/00Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M14/00Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005Photoelectrochemical storage cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/16Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/50Fuel cells
    • Y02E60/52Fuel cells characterised by type or design
    • Y02E60/527Bio Fuel Cells

Abstract

Provided is a battery comprising a first compartment, a second compartment and a barrier separating the first and second compartments, wherein the barrier comprises a proton transporting moiety.

Description

ENZYMATIC BATTERY

The present invention relates to batteries, including fuel cells and re-chargeable fuel cells, for use in powering electrical devices. Batteries such as fuel cells are useful for the direct conversion of chemical energy into electrical energy. Fuel cells are typically made up of three chambers separated by two porous electrodes. A fuel chamber serves to introduce a fuel, typically hydrogen gas, which can be generated in situ by "reforming" hydrocarbons such as methane with steam, so that the hydrogen contacts H O at the first electrode, where, when a circuit is formed between the electrodes, a reaction producing electrons and hydronium (H3O+) ions is catalyzed.

2H2O + H2 ^ 2H3O+ + 2e" (1)

A central chamber can comprise an electrolyte. The central chamber acts to convey hydronium ions from the first electrode to the second electrode. The second electrode provides an interface with a recipient molecule, typically oxygen, found in the third chamber. The recipient molecule receives the electrons conveyed by the circuit.

2H3O+ + 1/2 O2 + 2e" ^ 3H

The electrolyte element of the fuel cell can be, for example, a conductive polymer material such as a hydrated polymer containing sulfonic acid groups on perfluoroethylene side chains on a perfluoroethylene backbone such as Nafion™ (du Pont de Nemours, Wilmington, DE) or like polymers available from Dow Chemical Co., Midland, MI. Other electrolytes include alkaline solutions (such as 35 wt %, 50 wt % or 85 wt % KOH), acid solutions (such as concentrated phosphoric acid), molten electrolytes (such as molten metal carbonate), and solid electrolytes (such as solid oxides such as yttria (Y O3)-stabilized zirconia (ZrO2)). Liquid electrolytes are often retained in a porous matrix. Such fuel cells are described, for example, in "Fuel Cells," Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 1 1, pp. 1098-1 121.

These types of fuel cells typically operate at temperatures from about 80°C to about 1 ,000°C The shortcomings of the technology include short operational lifetimes due to catalyst poisoning from contaminants, high initial costs, and the practical restrictions on devices that operate at relatively high to extremely high temperatures. The present invention provides a fuel cell technology that employs molecules used in biological processes to create fuel cells that operate at moderate temperatures and without the presence of harsh chemicals maintained at high temperatures, which can lead to corrosion of the cell components. While the fuel used in the fuel cells of the invention are more complex, they are readily available and suitably priced for a number of applications, such as power supplies for mobile computing or telephone devices. It is anticipated that fuel cells of the invention can be configured such that a 300 cc cell has a capacity of as much as 80 W*h - and thus can have more capacity than a comparably sized battery for a laptop computer - and that such cells could have still greater capacity. Thus, it is believed that the fuel cells of the invention can be used to increase capacity, and/or decrease size and/or weight. Moreover, the compact, inert energy sources of the invention can be used to provide short duration electrical output. Since the materials retained within the fuel cells are non-corrosive and typically not otherwise hazardous, it is practical to recharge the fuel cells with fuel, with the recharging done by the consumer or through a service such as a mail order service. Moreover, in certain aspects, the invention provides fuel cells that use active transport of protons to increase sustainable efficiency. Fuel cells of the invention can also be electrically re-charged.

SUMMARY OF THE INVENTION In one aspect, the invention provides a fuel cell comprising a first compartment, a second compartment and a barrier separating the first and second compartments, wherein the barrier comprises a proton transporting moiety.

In another aspect, the invention provides a fuel cell a first compartment; a second compartment; a barrier separating the first compartment from the second compartment; a first electrode; a second electrode; a redox enzyme in the first compartment in communication with the first electrode to receive electrons therefrom, the redox enzyme incorporated in a lipid composition; an electron carrier in the first compartment in chemical communication with the redox enzyme; and an electron receiving composition in the second compartment in chemical communication with the second electrode, wherein, in operation, an electrical current flows along a conductive pathway formed between the first electrode and the second electrode. BRIEF DESCRIPTION OF THE DRAWING

Figure 1 displays a perspective view of the interior of a fuel cell with three chambers.

Figures 2 illustrates a fuel cell exhibiting certain preferred aspects of the present invention. Figure 3A, 3B and 3C illustrate a similar fuel cell with scavenger-containing segment.

Figures 4A and 4B show a top view of a fuel cell with two chambers.

Figure 5A shows a top view of a fuel cell with two chambers, while Figure 5B shows a side view. Figure 6 shows a fuel cell where the fluids bathing the two electrodes are segregated.

Figure 7 shows a fuel cell with incorporated light regulation and a sensor.

DEFINITIONS

The following terms shall have, for the purposes of this application, the respective meaning set forth below.

• electron carrier: An electron carrier is a composition that provides electrons in an enzymatic reaction. Electron carriers include, without limitation, reduced nicotinamide adenine dinucleotide (denoted NADH; oxidized form denoted NAD or NAD+), reduced nicotinamide adenine dinucleotide phosphate (denoted NADPH; oxidized form denoted NADP or NADP+), reduced nicotinamide mononucleotide (NMNH; oxidized form NMN), reduced flavin adenine dinucleotide (FADH2; oxidized form FAD), reduced flavin mononucleotide (FMNH2; oxidized form FMN), reduced coenzyme A, and the like. Electron carriers include proteins with incorporated electron-donating prosthetic groups, such as coenzyme A, protoporphyrin IX, vitamin B 12, and the like Further electron carriers include glucose (oxidized form: gluconic acid), alcohols (e.g., oxidized form: ethyl aldehyde), and the like. Preferably the electron carrier is present in a concentration of 1 M or more, more preferably 1.5 M or more, yet more preferably 2 M or more.

• electron-receiving composition: An electron-receiving composition receives the electrons conveyed to the cathode by the fuel cell. • electron transfer mediator: An electron transfer mediator is a composition which facilitates transfer to an electrode of electrons released from an electron carrier. • redox enzyme: An redox enzyme is one that catalyzes the transfer of electrons from an electron carrier to another composition, or from another composition to the oxidized form of an electron carrier. Examples of appropriate classes of redox enzymes include: oxidases, dehydrogenases, reductases and oxidoreductases. Additionally, other enzymes, will redox catalysis as their secondary property could also be used e.g., superoxide dismutase.

• composition. Composition refers to a molecule, compound, charged species, salt, polymer, or other combination or mixture of chemical entities.

Detailed Description Figure 1 illustrates features of an exemplary battery such as a fuel cell 10. The fuel cell 10 has a first chamber 1 containing an electron carrier, with the textured background fill of the first chamber 1 illustrating that the solution can be retained within a porous matrix (including a membrane). Second chamber 2 similarly contains an electrolyte (and can be the same material as found in the first chamber) in a space, which space can also be filled with a retaining matrix, intervening between porous first electrode 4 and porous second electrode 5. A face of second electrode 5 contacts the space of third chamber 3, into which an electron receiving molecule, typically a gaseous molecule such as oxygen, is introduced. First electrical contact 6 and second electrical contact 7 allow a circuit to be formed between the two electrodes. The optional porous retaining matrix can help retain solution in, for example, the second chamber 2 and minimize solution spillover into the third chamber 3, thereby maintaining a surface area of contact between the electron receiving molecule and the second electrode 5. In some embodiments, the aqueous liquid in the first chamber 1 and second chamber 2 suspends non-dissolved reduced electron carrier, thereby increasing the reservoir of reduced electron carrier available for use to supply electrons to the first electrode 4. In another example, where the chambers include a porous matrix, a saturated solution can be introduced, and the temperature reduced to precipitate reduced electron carrier within the pores of the matrix. Following precipitation, the solution phase can be replaced with another concentrated solution, thereby increasing the amount of electron carrier, which electron carrier is in both solid and solvated form.

It will be recognized that the second chamber can be made up of a polymer electrolyte, such as one of those described above. The reaction that occurs at the first electrode can be exemplified with NADH as follows:

H2O + NADH ^ NAD+ + H3O+ + 2e" (3)

Preferred enzymes relay the electrons to mediators that convey the electrons to the anode electrode. Thus, if the enzyme normally conveys the electrons to reduce a small molecule, this small molecule is preferably bypassed. The corresponding reaction at the second electrode is:

2H3O+ + 1/2 O2 + 2e~ ^ 3H2O (2)

Using reaction 2, preferably the bathing solution is buffered to account for the consumption of hydrogen ions, or hydrogen ion donating compounds must be supplied during operation of the fuel cell. This accounting for hydrogen ion consumption helps maintain the pH at a value that allows a useful amount of redox enzymatic activity. To avoid this issue, an alternate electron receiving molecule with an appropriate oxidation/reduction potential can be used. For instance, periodic acid can be used as follows: H3O+ + H5IO6 + 2e" ^ IO3 " + 4H2O (4)

The use of this reaction at the cathode results in a net production of water, which, if significant, can be dealt with, for example, by providing for space for overflow liquid. Such alternative electron receiving molecules are often solids at operating temperatures or solutes in a carrier liquid, in which case the third chamber 3 should be adapted to carry such non- gaseous material. Where, as with periodic acid, the electron receiving molecule can damage the enzyme catalyzing the electron releasing reaction, the second chamber 2 can have a segment, as illustrated as item 8 in fuel cell 10' of Figure 2, containing a scavenger for such electron receiving molecule.

In a preferred embodiment, the electrodes comprise metallizations on each side of a non-conductive substrate. For example, in Figure 3A the metallization on a first side of dielectric substrate 42 is the first electrode 44, while the metallization on the second side is the second electrode 45. Perforations 49 function as the conduit between the anode and cathode of the fuel cell, as discussed further below. The illustration of Figure 3A, it will be recognized, is illustrative of the relative geometry of this embodiment. The thickness of dielectric substrate 42 is, for example, from 15 micrometer (μm) to 50 micrometer, or from 15 micrometer to 30 micrometer. The width of the perforations is, for example, from 20 micrometer to 80 micrometer. Preferably, perforations comprise in excess of 50% of the area of any area of the dielectric substrate involved in transport between the chambers, such as from 50 to 75% of the area. In certain preferred embodiments, the dielectric substrate is glass or an polymer, such as polyvinyl acetate or soda lime silicate. Fig. 3B illustrates the electrodes framed on a perforated substrate in more detail. The perforations 49 together with the dielectric substrate 42 provide a support for lipid bilayers (i.e., membranes) spanning the perforations. Such lipid bilayers can incorporate at least a first enzyme or enzyme complex (hereafter "first enzyme") 62 effective (i) to oxidize the reduced form of an electron carrier, and preferably (ii) to transport, in conjunction with the oxidation, protons from the fuel side 41 to the product side 43 of the fuel cell 50. Preferably, the first enzyme 62 is immobilized in the lipid bilayer with the appropriate orientation to allow access of the catalytic site for the oxidative reaction to the fuel side and asymmetric pumping of protons. However, as the fuel is substantially isolated on the fuel side 41, an enzyme inserted into the lipid bilayer with the opposite orientation is without an energy source. Examples of particularly preferred enzymes providing one or both of the oxidation/reduction and proton pumping functions include, for example, NADH dehydrogenase (e.g., from E.coli. Tran et al., "Requirement for the proton pumping NADH dehydrogenase I of Escherichia coli in respiration of NADH to fumarate and its bioenergetic implications," Eur. J. Biochem. 244: 155, 1997), NADPH transhydrogenase, proton ATPase, and cytochrome oxidase and its various forms. Methods of isolating such an NADH dehydrogenase enzyme are described in detail, for example, in Braun et al., Biochemistry 37: 1861-1867, 1998; and Bergsma et al., "Purification and characterization of NADH dehydrogenase from Bacillus subtilis," Eur. J. Biochem. 128: 151-157, 1982. The lipid bilayer can be formed across the perforations 49 and enzyme incorporated therein by, for example, the methods described in detail in Niki et al., US Patent 4,541,908 (annealing cytochrome C to an electrode) and Persson et al., J. Electroanalytical Chem. 292: 115, 1990. Such methods can comprise the steps of: making an appropriate solution of lipid and enzyme, where the enzyme may be supplied to the mixture in a solution stabilized with a detergent; and, once an appropriate solution of lipid and enzyme is made, the perforated dielectric substrate is dipped into the solution to form the enzyme-containing lipid bilayers. Sonication or detergent dilution may be required to facilitate enzyme incorporation into the bilayer. See, or example, Singer, Biochemical Pharmacology 31 : 527-534, 1982; Madden, "Current concepts in membrane protein reconstitution," Chem. Phys. Lipids 40: 207-222, 1986; Montal et al., "Functional reassembly of membrane proteins in planar lipid bilayers," Quart. Rev. Biophys. 14: 1-79, 1981; Helenius et al., "Asymmetric and symmetric membrane reconstitution by detergent elimination," Eur. J. Biochem. 116: 27-31, 1981 ; Volumes on biomembranes (e.g., Fleischer and Packer (eds.)), in Methods in Enzymology series, Academic Press.

Using enzymes having both the oxidation/reduction and proton pumping functions, and which consume electron carrier, the acidification of the fuel side caused by the consumption of electron carrier is substantially offset by the export of protons. Net proton pumping in conjunction with reduction of an electron carrier can exceed 2 protons per electron transfer (e.g., up to 3 to 4 protons per electron transfer). Accordingly, in some embodiments care must be taken to buffer or accommodate excess de-acidification on the fuel side or excess acidification of the product side. Alternatively, the rate of transport is adjusted by incorporating a mix of redox enzymes, some portion of which enzymes do not exhibit coordinate proton transport. In some embodiments, care is taken especially on the fuel side to moderate proton export to match proton production. Acidification or de-acidification on one side or another of the fuel cell can also be moderated by selecting or mixing redox enzymes to provide a desired amount of proton production. Of course, proton export from the fuel side is to a certain degree self-limiting, such that in some embodiments the theoretical concern for excess pumping to the product side is of, at best, limited consequence. For example, mitochondrial matrix proteins which oxidize electron carriers and transport protons operate to create a substantial pH gradient across the inner mitochondrial membrane, and are designed to operate as pumping creates a relatively high pH such as pH 8 or higher. (In some embodiments, however, care is taken to keep the pH in a range closer to pH 7.4, where many electron carriers such as NADH are more stable.) Irrespective of how perfectly proton production is matched to proton consumption, the proton pumping provided by this embodiment of the invention helps diminish loses in the electron transfer rate due to a shortfall of protons on the product side.

In some embodiments, proton pumping is provided by a light-driven proton pump such as bacteriorhodopsin. Recombinant production of bacteriorhodopsin is described, for example, in Nassal et al., J. Biol. Chem. 262: 9264-70, 1987. All trans retinal is associated with bacteriorhodopsin to provide the light-absorbing chromophore. Light to power this type of proton pump can be provided by electronic light sources, such as LEDs, incorporated into the fuel cell and powered by a (i) portion of energy produced from the fuel cell, or (ii) a translucent portion of the fuel cell casing that allows light from room lighting or sunlight to impinge the lipid bilayer. For example, illustrated in Fig. 7 is a fuel cell 400 in which light control devices 71 are incorporated. These light control devices 71 contain, for example, LEDs or liquid crystal shutters. Liquid crystal shutters have a relatively opaque and a relatively translucent state and can be electronically switched between the two states. An eternal light source, such as the light provided by room lighting or sunlight can be regulated through the use of liquid crystal shutters or other shuttering device. In some embodiments, the light control devices are individually regulated or regulated in groups to aid in regulating the amount of light conveyed to the proton pump protein. Preferably, the light control devices 71 have lenses to direct the light to focus primarily at the dielectric substrate 42, particularly those portions containing lipid bilayers incorporating the proton pumps. A monitoring device 72 can operate to monitor a condition in the fuel cell, such as the pH or the concentration of electron carrier, and relay information to a controller 73 which operates to moderate an aspect of the operation of the fuel cell should monitored values dictate such action. For example, the controller 73 can moderate the level of light conveyed by the light control devices 71 depending upon the pH of the fuel side 41. Note that in one embodiment an external light source is allowed to energize the proton pump without the use of any light-regulating devices.

In another embodiment, redox enzyme is deposited on or adjacent to the first electrode, while a proton transporter is incorporated into the lipid bilayers of the perforations. In another embodiment, a second enzyme 63 is incorporated into the fuel cell, such as into the lipid bilayer or otherwise on the first electrode or in the first chamber, to facilitate proton transport or generation in the first chamber during recharge mode, thereby adding protons to the fuel side. The second enzyme can be the same as, or distinct from, the enzyme that transports protons during forward operation. An example of this second enzyme include transporting proteins with lower redox potential relative to, for example, NAD succinate dehydrogenase in conjunction with the CoQH2-cyt c reductase complex. Also useful are lactate dehydrogenase and malate dehydrogenase, both enzymes isolated from various sources available from Sigma Chemical Co., St. Louis, MO. For example, bacteriorhodopsin can also be used with an orientation appropriate for this use in the recharge mode. In some embodiments, the recharge mode operates to regenerate NADH, but does not reverse pump protons.

The perforations 49 are illustrated as openings. However, these can also comprise porous segments of the dielectric substrate 42. Alternatively, these can comprise membranes spanning the perforations 49 to support the lipid bilayer. Preferably, the perforations encompass a substantial portion of the surface area of the dielectric substrate, such as 50%. Preferably, enzyme density in the lipid bilayer is high, such as 2 x 1012/mm2.

The orientation of enzyme in the lipid bilayer can be random, with effectiveness of proton pumping dictated by the asymmetric presence of substrate such as protons and electron carrier. Alternatively, orientation is established for example by using antibodies to the enzyme present on one side of the membrane during formation of the enzyme-lipid bilayer complex.

The perforations 49 and metallized surfaces (first electrode 44 and second electrode 45) of the dielectric substrate 42 can be constructed, for example, with masking and etching techniques of photolithography well known in the art. Alternatively, the metallized surfaces (electrodes can be formed for example by (1) thin film deposition through a mask, (2) applying a blanket coat of metallization by thin film then photo-defining, selectively etching a pattern into the metallization, or (3) Photo-defining the metallization pattern directly without etching using a metal impregnated resist (DuPont Fodel process, see, Drozdyk et. al. "Photopatternable Conductor tapes for PDP applications" Society for Information Display 1999 Digest, 1044-1047; Nebe et al., US Patent 5,049,480). In one embodiment, the dielectric substrate is a film. For example, the dielectric can be a porous film that is rendered non-permeable outside the "perforations" by the metallizations. The surfaces of the metal layers can be modified with other metals, for instance by electroplating. Such electroplatings can be, for example, with chromium, gold, silver, platinum, palladium, nickel, mixtures thereof, or the like, preferably gold and platinum. In addition to metallized surfaces, the electrodes can be formed by other appropriate conductive materials, which materials can be surface modified. For example, the electrodes can be formed of carbon (graphite), which can be applied to the dielectric substrate by electron beam evaporation, chemical vapor deposition or pyrolysis. Preferably, surfaces to be metallized are solvent cleaned and oxygen plasma ashed. As illustrated in Figure 3C, electrical contact 54 connects the first electrode 44 to a prospective electrical circuit, while electrical contact 55 connects the second electrode 45.

In one embodiment, the product side of the fuel cell is comprised of an aqueous liquid with dissolved oxygen. In an embodiment, at least a portion of the wall retaining such aqueous liquid is oxygen permeable, but sufficiently resists transmission of water vapor to allow a useful product lifetime with the aqueous liquid retained in the fuel cell. An example of an appropriate polymeric wall material is an oxygen permeable plastic. In contrast, the fuel side is preferably constructed of material that resists the incursion of oxygen. The fuel cell can be made anaerobic by flushing to purge oxygen with an inert gas such as nitrogen or helium. In some rechargeable embodiments, the electron-receiving composition is regenerated during recharging mode, thereby eliminating or reducing the need for an outside supply of such electron-receiving composition.

The fuel cell of the invention can preferably be recharged by applying an appropriate voltage to inject electrons into the fuel side to allow the first enzyme to catalyze the reverse reaction. In particularly preferred embodiments, the first enzyme has both the oxidation/reduction and proton pumping functions and operates to reverse pump protons from the product side to the fuel side during recharging. Thus, the reverse pumping supplies the protons consumed in generating, for example, NADH from (i) NAD+ and (ii) the injected electrons and protons. Note that in reverse operation the injected electrons act first to reduce any oxygen resident in the fuel side, as this reaction is energetically favored. Once any such oxygen is consumed, the electrons can contribute to regenerating the reduced electron carrier.

The above discussion of the embodiments using proton transport focus on the use of both faces of a substrate to provide the electrodes, thereby facilitating a more immediate transfer of protons to the product side where the protons are consumed in reducing the electron-receiving composition. However, it will be recognized that in this embodiment structures such as a porous matrix can be interposed between the fuel side and the product side. Such an intervening structure can operate to provide temperature shielding or scavenger molecules that protect, for example, the enzymes from reactive compounds.

The fuel cell operates within a temperature range appropriate for the operation of the redox enzyme. This temperature range typically varies with the stability of the enzyme, and the source of the enzyme. To increase the appropriate temperature range, one can select the appropriate redox enzyme from a thermophilic organism, such as a microorganism isolated from a volcanic vent or hot spring. Nonetheless, preferred temperatures of operation of at least the first electrode are about 80°C or less, preferably 60°C or less, more preferably 40°C or 30°C or less. The porous matrix is, for example, made up of inert fibers such as asbestos, sintered materials such as sintered glass or beads of inert material. The first electrode (anode) can be coated with an electron transfer mediator such as an organometallic compound which functions as a substitute electron recipient for the biological substrate of the redox enzyme. Similarly, the lipid bilayer of the embodiment of Fig. 3 or structures adjacent to the bilayer can incorporate such electron transfer mediators. Such organometallic compounds can include, without limitation, dicyclopentadienyliron (CιoHι0Fe, ferrocene), available along with analogs that can be substituted, from Aldrich, Milwaukee, WI, platinum on carbon, and palladium on carbon. Further examples include ferredoxin molecules of appropriate oxidation/reduction potential, such as the ferredoxin formed of rubredoxin and other ferredoxins available from Sigma Chemical . Other electron transfer mediators include organic compounds such as quinone and related compounds. The electron transfer mediator can be applied, for example, by screening or masked dip coating or sublimation. The first electrode can be impregnated with the redox enzyme, which can be applied before or after the electron transfer mediator. One way to assure the association of the redox enzyme with the electrode is simply to incubate a solution of the redox enzyme with electrode for sufficient time to allow associations between the electrode and the enzyme, such as Van der Waals associations, to mature. Alternatively, a first binding moiety, such as biotin or its binding complement avidin/streptavidin, can be attached to the electrode and the enzyme bound to the first binding moiety through an attached molecule of the binding complement.

The redox enzyme can comprise any number of enzymes that use an electron carrier as a substrate, irrespective of whether the primary biologically relevant direction of reaction is for the consumption or production of such reduced electron carrier, since such reactions can be conducted in the reverse direction. Examples of redox enzymes further include, without limitation, glucose oxidase (using NADH, available from several sources, including number of types of this enzyme available from Sigma Chemical), glucose-6-phosphate dehydrogenase (NADPH, Boehringer Mannheim, Indianapolis, IN), 6-phosphogluconate dehydrogenase (NADPH, Boehringer Mannheim), malate dehydrogenase (NADH, Boehringer Mannheim), glyceraldehyde-3-phosphate dehydrogenase (NADH, Sigma, Boehringer Mannheim), isocitrate dehydrogenase (NADH, Boehringer Mannheim; NADPH, Sigma), and α- ketoglutarate dehydrogenase complex (NADH, Sigma).

The redox enzyme can also be a transmembrane pump, such as a proton pump, that operates using an electron carrier as the energy source. In this case, enzyme can be associated with the electrode in the presence of detergent and/or lipid carrier molecules which stabilize the active conformation of the enzyme. As in other embodiments, an electron transfer mediator can be used to increase the efficiency of electron transfer to the electrode.

Associated electron carriers are readily available from commercial suppliers such as Sigma and Boehringer Mannheim. The concentrations at which the reduced form of such electron carriers can be as high as possible without disrupting the function of the redox enzyme. The salt and buffer conditions are designed based on, as a starting point, the ample available knowledge of appropriate conditions for the redox enzyme. Such enzyme conditions are typically available, for example, from suppliers of such enzymes.

As illustrated for the fuel cell 100 in Figure 4A (top view), a source reservoir 111 can be provided to supply reduced electron carrier via conduit 113, check-valve 112 and diffuser 114 to second chamber 102. Note that fuel cell 100 lacks a first chamber as this chamber often serves as a reservoir, which in fuel cell 100 is provided by source reservoir 111. Diffuser 115, conduit 116, and pump 117 provide the pathway and motive power for conveying spent liquid containing the electron carrier (often merely having reduced effectiveness in powering the fuel cell) to an output reservoir 118. Fuel cell 100 further has a first electrode 104, second electrode 105, third chamber 103, air pump 121, air inlet 122, and air outlet 123. The various pumps can be operated off of a battery, which can be recharged and regulated using energy from the fuel cell, or can come into operation after the fuel cell begins generating current. As illustrated in Figure 4B, voltage or current monitor M can monitor the performance the fuel cell in providing voltage to the circuit comprising resister(s) R. Monitor M can relay information to the controller, which uses the information to regulate operation of one or more of the pumps.

Figure 5A illustrates a fuel cell 200 (top view) in which an acid/base reservoir 231 serves to supply a source of a material required to account for any material imbalances in the reaction equations at the first and second electrodes. The acid/base reservoir 231 is connected via conduit 232, first actuated valve 233, and diffuser 234 to a second chamber 202. Liquid from source reservoir 211 is delivered via check valve 212A and second actuated valve 212B. In one example of operation, second actuated valve 212B is normally open, and first actuated valve 233 is normally closed. These valve positions are reversed when the controller detects the need for fluid from acid/base reservoir 231 (e.g., because of a signal received from a pH monitor) and operates pump 117 (e.g., by use of a stepper motor) to draw fluid into the second chamber 202.

It will be recognized that the pump and valve arrangements in Figures 4A through 5B are for illustration only, as numerous alternative arrangements will be recognized by those of ordinary skill. The plumbing of the fuel cell can be arranged to maintain a chamber less than atmospheric pressure, for instance to help reduce fluid leakage through various porous materials. The pores in various porous materials can be selected to allow such diffusion as is needed while minimizing fluid flow across the porous materials, such as bulk liquid flow into a chamber designed to bring gas into contact with a porous electrode.

The chambers of fluid which the first and second electrodes contact can be independent, as illustrated in Figure 6. In fuel cell 300, the solution bathing the first electrode (anode) is fed through conduit 313A, while that bathing the second electrode

(cathode) is supplied through conduit 313B. Flow is illustrated as regulated by pumps 317A and 317B. In the illustrated fuel cell, the bathing solutions are replenished as needed to account for the necessary imbalance in the chemistries occurring in the segregated cells. Cells can be stacked, and electrodes arranged in a number of ways to increase the areas of contact between electrodes and reactants. These stacking and arranging geometries can be based on well-known geometries used with conventional fuel cells.

It will be recognized that where the electron carrier has an appropriate electrochemical potential relative to the electron-receiving molecule, the cell can be operated so that the oxidized form of the electron carrier receives the electrons through an enzyme catalyzed event. For example, the electron carrier and the electron-receiving molecule can both be of the class exemplified for electron carriers, but with distinct electrochemical potentials. Thus, both the fuel side and product side reactions can be enzyme catalyzed. In fact, even with such traditional electron-receiving composition as oxygen, the product side reaction can be enzyme catalyzed. In one embodiment of the invention, the fuel cell does not incorporate a proton pump.

Preferably, in this embodiment the redox enzyme is associated with a lipid component, such as a composition containing phospholipid, steroids (such as sterols), glycolipids, sphinoglipids, triglyceride or other components typically incorporated into intracellular or external cellular membranes, while still being sufficiently associated with the electrodes to convey electrons. The enzyme is preferably incorporated into a lipid bilayer. The barrier can be separating component such as is used in a typical fuel cell, which preferably conveys protons between the first and second chambers, though without requiring proton pumping.

The following examples further illustrate the present invention, but of course, should not be construed as in any way limiting its scope. Example

The test apparatus consisted of a 5 ml reaction vessel which held the fuel and into which copper or other electrodes were dipped. The electrodes were in turn connected to a high impedance voltmeter for open circuit voltage measurements or to a low impedance ammeter for short circuit current measurements. Various test configurations were employed to establish a baseline with which to measure performance of the cell. Testing was done by dipping electrodes in the fuel solution and measuring current and / or voltage as a function of time.

The reaction which drove the cell was the oxidation of nicotinamide-adenine dinucleotide hydride (NADH) which is catalyzed by the enzyme glucose oxidase (GOD) in the presence of glucose. This reaction yielded NAD+, a proton (H+) and 2 free electrons.

H20 + NADH = NAD+ + H30+ + 2e~ The reaction toke place at one electrode, which was a metallized plastic strip coated with the enzyme GOD. This half-reaction was coupled through an external circuit to the formation of water or hydrogen peroxide from protons, dissolved oxygen, and free electrons at the other electrode.

Fuels used were solutions of glucose, NADH or combinations thereof, distilled deionized water or a 50 mM solution of Tris™ 7.4 buffer. (NADH is most stable in a pH 7.4 environment.) Electrode materials were copper (as a reference) and metallized plastic strips coated with GOD (a commercially available product).

Test configurations employed as well as initial results were as follows: Configuration 1: Electrode 1 : Copper

Electrode 2: Copper Solution: 50 mM tris 7.4 buffer Voltage: -7.5 mV

Current: 3 μA initially decaying to -2.2 μA within 3 minutes, fairly constant thereafter. Configuration 2: Electrode 1: Copper

Electrode 2: GOD coated strip Solution: 50 mM tris 7.4 buffer Voltage: + 350 mV

Current: > 20 μA (+) initially decaying to + 4 μA within 2 minutes, fairly constant thereafter.

Configuration 3:

Electrode 1 : Copper Electrode 2: Copper

Solution: 10 mM glucose in 50 mM tris 7.4 buffer Voltage: -6.3 mVCurrent: -1.7 μA, fairly constant after initial dropoff.

Configuration 4:

Electrode 1 : Copper Electrode 2: GOD coated strip Solution: 10 mM glucose in 50 mM tris 7.4 buffer Voltage: + 350 mV

Current: > 20 μA (+) initially decaying to ~ + 2 μA within 2 minutes, fairly constant thereafter. Configuration 5:

Electrode 1 : Copper Electrode 2: Copper

Solution: 10 mM glucose + 10 mM NADH in 50 mM tris 7.4 buffer Voltage: -290 mV slowly increasing to - 320 after 4 minutes Current: -25 μA, decaying to -21 μA after 2 minutes. Configuration 6: Electrode 1 : Copper

Electrode 2: GOD coated strip

Solution: 10 mM glucose + 10 mM NADH in 50 mM tris 7.4 buffer Voltage: + 500 mV decaying to +380 after 2 minutes

Current: > + 30 μA, dropping rapidly to ~ + 1 μA after 1 minute.

All publications and references, including but not limited to patents and patent applications, cited in this specification are herein incorporated by reference in their entirety as if each individual publication or reference were specifically and individually indicated to be incorporated by reference herein as being fully set forth. Any patent application to which this application claims priority is also incorporated by reference herein in its entirety in the manner described above for publications and references. While this invention has been described with an emphasis upon preferred embodiments, it will be obvious to those of ordinary skill in the art that variations in the preferred devices and methods may be used and that it is intended that the invention may be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications encompassed within the spirit and scope of the invention as defined by the claims that follow.

Claims

What is claimed:
1. A battery comprising a first compartment, a second compartment and a barrier separating the first and second compartments, wherein the barrier comprises a proton transporting moiety.
2. A battery comprising: a first compartment; a second compartment; a barrier separating the first compartment from the second compartment; said barrier having a proton transporting moiety; a first electrode; a second electrode; a redox enzyme in the first compartment in communication with the first electrode to receive electrons therefrom; an electron carrier in the first compartment in chemical communication with the redox enzyme; and an electron receiving composition in the second compartment in chemical communication with the second electrode, wherein, in operation, an electrical current flows along a conductive pathway formed between the first electrode and the second electrode.
3. The battery of claim 2, wherein the first electrode is further associated with an electron transfer mediator that transfers electrons from the redox enzyme to the first electrode.
4. The battery of claim 2, wherein the proton transporting protein comprises at least a portion of the redox enzyme.
5. The battery of claim 2, further comprising a reservoir for supplying to the vicinity of at least one of the electrodes a component consumed in the operation of the battery and a pump for drawing such component to that vicinity.
6. The battery of claim 5, further comprising a controller which receives data on the operation of the battery and controls the pump in response to the data.
7. The battery of claim 2, wherein a light-driven proton pump protein comprises at least a portion of the proton transporting protein, and further comprising: a source of light for powering the light-driven proton pump protein.
8. The battery of claim 2, further incorporating in the barrier a second protein, distinct from the first, adapted to facilitate reverse proton pumping when the battery is operated in recharge mode.
9. A method of operating a battery with a first compartment and a second compartment comprising: enzymatically oxidizing an electron carrier and delivering the electrons to a first electrode in chemical communication with the first compartment; catalyzing the transfer of protons from the first compartment to the second compartment; and reducing an electron receiving molecule with electrodes conveyed through a circuit from the first electrode to a second electrode located in the second compartment.
10. The method of claim 9, wherein the catalytic transfer of protons occurs in conjunction with the enzymatic oxidation of the electron carrier.
1 1. The method of claim 9, wherein at least a portion of the transfer of protons is driven by a light-driven proton pump protein, and the method further comprises: directing light to the light-driven proton pump.
12. The method of claim 11 , further comprising monitoring the pH of the first compartment and controlling the amount of light directed to the light-driven proton pump such that relatively more light is directed at lower pH values.
13. The method of claim 9, further comprising: applying a voltage to the electrodes of a polarity opposite that generated by the normal operation of the battery to recharge the battery.
14. The method of claim 13, further comprising: enzymatically transporting protons from the second chamber to the first chamber in connection with the applying the recharge voltage.
15. The method of claim 14, wherein at least a portion of the enzymatic transport in recharge mode is accomplished by an enzyme distinct from an enzyme catalyzing the majority of proton transport in a power producing mode.
16. A battery comprising: a first compartment; a second compartment; a barrier separating the first compartment from the second compartment; a first electrode; a second electrode; a redox enzyme in the first compartment in communication with the first electrode to receive electrons therefrom, the redox enzyme incorporated in a lipid composition; an electron carrier in the first compartment in chemical communication with the redox enzyme; and an electron receiving composition in the second compartment in chemical communication with the second electrode, wherein, in operation, an electrical current flows along a conductive pathway formed between the first electrode and the second electrode.
17. A method of operating a battery with a first compartment and a second compartment comprising: enzymatically oxidizing, with an enzyme incorporated into a lipid composition, an electron carrier and delivering the electrons to a first electrode in chemical communication with the first compartment; and reducing an electron receiving molecule with electrodes conveyed through a circuit from the first electrode to a second electrode located in the second compartment.
PCT/US1999/018804 1998-08-19 1999-08-19 Enzymatic battery WO2000022688A9 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US9727798 true 1998-08-19 1998-08-19
US60/097,277 1998-08-19
US11883799 true 1999-02-05 1999-02-05
US60/118,837 1999-02-05
US12602999 true 1999-03-25 1999-03-25
US60/126,029 1999-03-25
US13424099 true 1999-05-14 1999-05-14
US60/134,240 1999-05-14
US09/376,792 1999-08-18
US09376792 US6500571B2 (en) 1998-08-19 1999-08-18 Enzymatic fuel cell

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2000576504A JP2002527874A (en) 1998-08-19 1999-08-19 Enzyme battery
AU2586200A AU764934B2 (en) 1998-08-19 1999-08-19 Enzymatic battery
MXPA01001792A MXPA01001792A (en) 1998-08-19 1999-08-19 Enzymatic battery.
NZ50983999A NZ509839A (en) 1998-08-19 1999-08-19 Enzymatic battery
CA 2340980 CA2340980A1 (en) 1998-08-19 1999-08-19 Enzymatic battery
IL14139399A IL141393D0 (en) 1998-08-19 1999-08-19 Enzymatic battery
BR9913087A BR9913087A (en) 1998-08-19 1999-08-19 enzymatic battery
EP19990968444 EP1110261A2 (en) 1998-08-19 1999-08-19 Enzymatic battery
NO20010797A NO20010797A (en) 1998-08-19 2001-02-16 Enzyme battery

Publications (3)

Publication Number Publication Date
WO2000022688A2 true WO2000022688A2 (en) 2000-04-20
WO2000022688A3 true WO2000022688A3 (en) 2000-09-21
WO2000022688A9 true true WO2000022688A9 (en) 2000-11-09

Family

ID=27536829

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/018804 WO2000022688A9 (en) 1998-08-19 1999-08-19 Enzymatic battery

Country Status (6)

Country Link
US (3) US6500571B2 (en)
EP (1) EP1110261A2 (en)
JP (1) JP2002527874A (en)
CN (1) CN1336017A (en)
CA (1) CA2340980A1 (en)
WO (1) WO2000022688A9 (en)

Families Citing this family (89)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294281B1 (en) * 1998-06-17 2001-09-25 Therasense, Inc. Biological fuel cell and method
US20060292041A1 (en) * 2000-03-23 2006-12-28 Dugas Matthew P Solid state membrane channel device for the measurement and characterization of atomic and molecular sized samples
US6616895B2 (en) * 2000-03-23 2003-09-09 Advanced Research Corporation Solid state membrane channel device for the measurement and characterization of atomic and molecular sized samples
DE10025033A1 (en) * 2000-05-20 2001-11-29 Dmc2 Degussa Metals Catalysts A method for electric power generation using a fuel cell
US6599441B1 (en) * 2000-07-18 2003-07-29 Emerald Biostructures, Inc. Crystallization solutions
GB0020051D0 (en) * 2000-08-16 2000-10-04 Mat & Separations Tech Int Ltd Improved fuel cell structure
US6824899B2 (en) * 2000-11-22 2004-11-30 Mti Microfuel Cells, Inc. Apparatus and methods for sensor-less optimization of methanol concentration in a direct methanol fuel cell system
US20030031911A1 (en) * 2001-04-13 2003-02-13 Rosalyn Ritts Biocompatible membranes and fuel cells produced therewith
CA2470107A1 (en) * 2001-12-11 2003-07-03 Powerzyme, Inc. Stabilized biocompatible membranes of block copolymers and fuel cells produced therewith
WO2002086999A1 (en) * 2001-04-13 2002-10-31 Powerzyme, Inc Enzymatic fuel cell
US20030113606A1 (en) * 2001-04-13 2003-06-19 Rosalyn Ritts Biocompatible membranes of block copolymers and fuel cells produced therewith
US20030049511A1 (en) * 2001-04-13 2003-03-13 Rosalyn Ritts Stabilized biocompatible membranes of block copolymers and fuel cells produced therewith
US7005273B2 (en) * 2001-05-16 2006-02-28 Therasense, Inc. Method for the determination of glycated hemoglobin
US6863833B1 (en) * 2001-06-29 2005-03-08 The Board Of Trustees Of The Leland Stanford Junior University Microfabricated apertures for supporting bilayer lipid membranes
JP3659582B2 (en) * 2001-11-20 2005-06-15 本田技研工業株式会社 The fuel circuit of the fuel cell system
FR2835655B1 (en) * 2002-02-07 2004-03-12 Commissariat Energie Atomique Fuel cell, using enzymes as catalysts of reactions cathodic and / or anodic
JP2005522692A (en) * 2002-04-05 2005-07-28 パワーザイム,インコーポレイテッド Analyte sensor
US20030198859A1 (en) * 2002-04-15 2003-10-23 Rosalyn Ritts Enzymatic fuel cell
US7368190B2 (en) 2002-05-02 2008-05-06 Abbott Diabetes Care Inc. Miniature biological fuel cell that is operational under physiological conditions, and associated devices and methods
FI119267B (en) * 2002-06-28 2008-09-15 Enfucell Oy A biocatalytic direct alcohol fuel cell
EP1531512A4 (en) * 2002-07-26 2010-08-11 Sony Corp Fuel battery
JP5207576B2 (en) * 2002-07-26 2013-06-12 ソニー株式会社 Fuel cells, portable power supply and electronic equipment
US20040146430A1 (en) * 2002-10-15 2004-07-29 Dugas Matthew P. Solid state membrane channel device for the measurement and characterization of atomic and molecular sized samples
US7638228B2 (en) * 2002-11-27 2009-12-29 Saint Louis University Enzyme immobilization for use in biofuel cells and sensors
WO2004071961A3 (en) 2003-02-13 2004-12-23 Baruch Berliner Water filter device and method
FR2854128B1 (en) * 2003-04-22 2006-04-07 Airbus France The flight control indicator for an aircraft, in particular a transport aircraft for providing the thrust generated by at least one engine of the aircraft
US7160637B2 (en) 2003-05-27 2007-01-09 The Regents Of The University Of California Implantable, miniaturized microbial fuel cell
NL1024378C2 (en) * 2003-09-25 2005-03-29 Pacques Bv A method for the generation of electrical energy from organic material; biofuel and electrode system.
US8859151B2 (en) * 2003-11-05 2014-10-14 St. Louis University Immobilized enzymes in biocathodes
US7241521B2 (en) * 2003-11-18 2007-07-10 Npl Associates, Inc. Hydrogen/hydrogen peroxide fuel cell
US7709134B2 (en) * 2004-03-15 2010-05-04 St. Louis University Microfluidic biofuel cell
US20050218398A1 (en) * 2004-04-06 2005-10-06 Availableip.Com NANO-electronics
US7019391B2 (en) * 2004-04-06 2006-03-28 Bao Tran NANO IC packaging
US7330369B2 (en) * 2004-04-06 2008-02-12 Bao Tran NANO-electronic memory array
US7671398B2 (en) 2005-02-23 2010-03-02 Tran Bao Q Nano memory, light, energy, antenna and strand-based systems and methods
US20050218397A1 (en) * 2004-04-06 2005-10-06 Availableip.Com NANO-electronics for programmable array IC
US7862624B2 (en) 2004-04-06 2011-01-04 Bao Tran Nano-particles on fabric or textile
CN100486020C (en) 2004-06-07 2009-05-06 索尼株式会社 Fuel cell, electronic equipment, movable body, power generation system and thermoelectricity combination system
US7410709B2 (en) * 2004-06-24 2008-08-12 Purdue Research Foundation Bio-battery
WO2006009324A1 (en) * 2004-07-23 2006-01-26 Canon Kabushiki Kaisha Enzyme electrode, and device, sensor, fuel cell and electrochemical reactor employing the enzyme electrode
WO2006015392A3 (en) * 2004-08-03 2006-03-09 Bhp Billiton Sa Ltd Enzymatic fuel cell
US7557433B2 (en) 2004-10-25 2009-07-07 Mccain Joseph H Microelectronic device with integrated energy source
US20060147763A1 (en) * 2004-12-30 2006-07-06 Angenent Largus T Upflow microbial fuel cell (UMFC)
GB0505087D0 (en) * 2005-03-12 2005-04-20 Acal Energy Ltd Fuel cells
US7264962B1 (en) * 2005-03-14 2007-09-04 Sandia Corporation Enzymatic cascade bioreactor
WO2006132595A1 (en) * 2005-06-04 2006-12-14 Agency For Science, Technology And Research Laminated battery
US20070048577A1 (en) * 2005-08-30 2007-03-01 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Naval Re Scalable microbial fuel cell with fluidic and stacking capabilities
CA2621658C (en) * 2005-09-15 2012-10-23 Sweet Power Inc. Microbial fuel cell with flexible substrate and micro-pillar structure
CN101366137A (en) * 2005-11-02 2009-02-11 圣路易斯大学 Enzymes immobilized in hydrophobically modified polysaccharides
US8415059B2 (en) * 2005-11-02 2013-04-09 St. Louis University Direct electron transfer using enzymes in bioanodes, biocathodes, and biofuel cells
US7885698B2 (en) 2006-02-28 2011-02-08 Abbott Diabetes Care Inc. Method and system for providing continuous calibration of implantable analyte sensors
GB0605878D0 (en) 2006-03-24 2006-05-03 Acal Energy Ltd Fuel cells
GB0608079D0 (en) 2006-04-25 2006-05-31 Acal Energy Ltd Fuel cells
US7393699B2 (en) 2006-06-12 2008-07-01 Tran Bao Q NANO-electronics
FI20060602A0 (en) * 2006-06-19 2006-06-19 Valtion Teknillinen New thin-film structures
WO2008082694A3 (en) * 2006-07-14 2009-02-05 Akermin Inc Organelles in bioanodes, biocathodes, and biofuel cells
GB0614338D0 (en) * 2006-07-19 2006-08-30 Acal Energy Ltd Fuel cells
GB0614337D0 (en) 2006-07-19 2006-08-30 Acal Energy Ltd Fuel Cells
US20080193802A1 (en) * 2006-08-09 2008-08-14 Mobilab Technologies Inc. Protein-coupled bioelectric solar cell
US8048547B2 (en) 2006-11-01 2011-11-01 The United States Of America, As Represented By The Secretary Of The Navy Biological fuel cells with nanoporous membranes
US20110039164A1 (en) * 2006-11-06 2011-02-17 Akermin, Inc. Bioanode and biocathode stack assemblies
WO2009009172A3 (en) * 2007-03-30 2009-04-16 Muinsh V Inamdar Biological battery or fuel cell utilizing mitochondria
WO2009003936A3 (en) * 2007-06-29 2009-04-30 Philippe Cinquin Biomimetic artificial membrane device
US7816024B2 (en) * 2007-07-09 2010-10-19 Advanced Ceramics Manufacturing, Llc Power generation device utilizing living plant nutrients
JP5298479B2 (en) * 2007-08-17 2013-09-25 ソニー株式会社 Fuel cell and electronic equipment
CA2699315A1 (en) * 2007-09-17 2009-03-26 Red Ivory Llc Self-actuating signal producing detection devices and methods
GB0718349D0 (en) 2007-09-20 2007-10-31 Acal Energy Ltd Fuel cells
GB0718577D0 (en) 2007-09-24 2007-10-31 Acal Energy Ltd Fuel cells
US20110076736A1 (en) * 2007-12-06 2011-03-31 Sony Corporation Fuel cell, method for manufacturing fuel cell, electronic apparatus, enzyme immobilization electrode, biosensor, bioreactor, energy conversion element, and enzyme reaction-utilizing apparatus
GB0801199D0 (en) 2008-01-23 2008-02-27 Acal Energy Ltd Fuel cells
GB0801195D0 (en) * 2008-01-23 2008-02-27 Acal Energy Ltd Fuel cells
GB0801198D0 (en) 2008-01-23 2008-02-27 Acal Energy Ltd Fuel cells
EP2287956A4 (en) * 2008-05-15 2012-07-25 Sony Corp Fuel cell, method for production of fuel cell, electronic device, enzyme-immobilized electrode, biosensor, bioreactor, energy conversion element, and enzymatic reaction-utilizing apparatus
US8722226B2 (en) 2008-06-12 2014-05-13 24M Technologies, Inc. High energy density redox flow device
US9786944B2 (en) * 2008-06-12 2017-10-10 Massachusetts Institute Of Technology High energy density redox flow device
US7807303B2 (en) * 2008-06-30 2010-10-05 Xerox Corporation Microbial fuel cell and method
US8304120B2 (en) * 2008-06-30 2012-11-06 Xerox Corporation Scalable microbial fuel cell and method of manufacture
JP5158513B2 (en) * 2008-12-19 2013-03-06 株式会社デンソー Fuel property sensor
US20100213057A1 (en) 2009-02-26 2010-08-26 Benjamin Feldman Self-Powered Analyte Sensor
US8778552B2 (en) 2009-04-06 2014-07-15 24M Technologies, Inc. Fuel system using redox flow battery
DK2544582T3 (en) 2010-03-11 2017-03-27 F Hoffmann-La Roche Ag A process for the electrochemical measurement of an analyte concentration in vivo, and fuel cell for this purpose
JP2011238501A (en) * 2010-05-12 2011-11-24 Sony Corp Fuel cell
US9084859B2 (en) 2011-03-14 2015-07-21 Sleepnea Llc Energy-harvesting respiratory method and device
US9484569B2 (en) 2012-06-13 2016-11-01 24M Technologies, Inc. Electrochemical slurry compositions and methods for preparing the same
CA2923794A1 (en) * 2012-09-09 2014-03-13 Biocheminsights, Inc. Electrochemical bioreactor module and methods of using the same
US8993159B2 (en) 2012-12-13 2015-03-31 24M Technologies, Inc. Semi-solid electrodes having high rate capability
US9362583B2 (en) 2012-12-13 2016-06-07 24M Technologies, Inc. Semi-solid electrodes having high rate capability
US9647289B1 (en) * 2014-02-19 2017-05-09 Haskell Dighton Unit for glucose depletion
EP3212821A4 (en) * 2014-11-02 2018-08-08 Biocheminsights Inc Improved electrochemical bioreactor module and use thereof

Family Cites Families (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3331705A (en) * 1962-07-11 1967-07-18 Mobil Oil Corp Biochemical fuel cell
US3811950A (en) 1972-01-26 1974-05-21 R Dibella Biochemical fuel cell and method of operating same
US4251631A (en) 1978-02-23 1981-02-17 Research Products Rehovot Ltd. Cross-linked enzyme membrane
US4117202A (en) 1976-11-12 1978-09-26 Beck Timothy A Solar powered biological fuel cell
FR2391467B1 (en) 1977-05-20 1981-09-11 Anvar
JPS5912135B2 (en) * 1977-09-28 1984-03-21 Matsushita Electric Ind Co Ltd
JPS5722193B2 (en) 1978-05-26 1982-05-12
WO1980000453A1 (en) 1978-08-15 1980-03-20 Nat Res Dev Enzymatic processes
DE3279215D1 (en) 1981-04-08 1988-12-15 Jagfeldt Hans Electrode for the electrochemical regeneration of co-enzyme, a method of making said electrode, and the use thereof
JPS6322024B2 (en) 1981-06-12 1988-05-10 Ajinomoto Kk
US4390603A (en) * 1981-06-30 1983-06-28 Hitachi, Ltd. Methanol fuel cell
US4581336A (en) 1982-04-26 1986-04-08 Uop Inc. Surface-modified electrodes
US4578323A (en) 1983-10-21 1986-03-25 Corning Glass Works Fuel cell using quinones to oxidize hydroxylic compounds
JPH0374468B2 (en) 1984-03-07 1991-11-27
GB8418775D0 (en) 1984-07-24 1984-08-30 Queen Elizabeth College Operation of microbial fuel cells
US5217900A (en) 1984-08-18 1993-06-08 Basf Aktiengesellschaft Biological reactor
GB8612861D0 (en) 1986-05-27 1986-07-02 Cambridge Life Sciences Immobilised enzyme biosensors
US5002871A (en) 1986-08-18 1991-03-26 The Coca-Cola Company Enzymatic membrane method for the synthesis and separation of peptides
US5336601A (en) 1986-08-18 1994-08-09 The Coca-Cola Company Enzymatic membrane method for the snythesis and separation of peptides
US5350681A (en) 1986-08-18 1994-09-27 The Coca-Cola Company Enzymatic membrane method for the synthesis and separation of peptides
US5238613A (en) * 1987-05-20 1993-08-24 Anderson David M Microporous materials
DE3852036D1 (en) 1987-07-27 1994-12-08 Commw Scient Ind Res Org Receptor membranes.
GB8817421D0 (en) 1988-07-21 1988-08-24 Medisense Inc Bioelectrochemical electrodes
US5211984A (en) 1991-02-19 1993-05-18 The Regents Of The University Of California Membrane catalyst layer for fuel cells
US5234777A (en) 1991-02-19 1993-08-10 The Regents Of The University Of California Membrane catalyst layer for fuel cells
US5206097A (en) 1991-06-05 1993-04-27 Motorola, Inc. Battery package having a communication window
US5264092A (en) 1991-10-02 1993-11-23 Moltech Corporation Redox polymer modified electrode for the electrochemical regeneration of coenzyme
EP0637384B1 (en) 1992-04-22 1996-10-02 Ecole Polytechnique Federale De Lausanne Lipid membrane sensors
DE69331333T2 (en) 1992-10-01 2002-08-14 Au Membrane & Biotech Res Inst Improved sensor membranes
US5477155A (en) 1993-08-11 1995-12-19 Millipore Corporation Current flow integrity test
US5773162A (en) 1993-10-12 1998-06-30 California Institute Of Technology Direct methanol feed fuel cell and system
US5599638A (en) 1993-10-12 1997-02-04 California Institute Of Technology Aqueous liquid feed organic fuel cell using solid polymer electrolyte membrane
US5393615A (en) 1994-02-03 1995-02-28 Miles Inc. Mediators suitable for the electrochemical regeneration of NADH, NADPH or analogs thereof
JP2570621B2 (en) 1994-06-27 1997-01-08 日本電気株式会社 A manufacturing method thereof, and a cell array forming method for cell culture substrate and
US5498542A (en) 1994-09-29 1996-03-12 Bayer Corporation Electrode mediators for regeneration of NADH and NADPH
EP1507303A1 (en) 1994-10-18 2005-02-16 California Institute Of Technology Organic fuel cell with improved membranes
DE4444893A1 (en) 1994-12-16 1996-06-20 Merck Patent Gmbh Peptides and synthetic membranes
US5547551A (en) 1995-03-15 1996-08-20 W. L. Gore & Associates, Inc. Ultra-thin integral composite membrane
US5662717A (en) 1995-05-05 1997-09-02 Rayovac Corporation Metal-air cathode can having reduced corner radius and electrochemical cells made therewith
US6087030A (en) 1995-05-05 2000-07-11 Rayovac Corporation Electrochemical cell anode and high discharge rate electrochemical cell employing same
US5520786A (en) 1995-06-06 1996-05-28 Bayer Corporation Mediators suitable for the electrochemical regeneration of NADH, NADPH or analogs thereof
US5672438A (en) 1995-10-10 1997-09-30 E. I. Du Pont De Nemours And Company Membrane and electrode assembly employing exclusion membrane for direct methanol fuel cell
US5795496A (en) 1995-11-22 1998-08-18 California Institute Of Technology Polymer material for electrolytic membranes in fuel cells
US5736026A (en) 1996-02-05 1998-04-07 Energy Research Corporation Biomass-fuel cell cogeneration apparatus and method
US6187231B1 (en) 1996-10-01 2001-02-13 Celanese Ventures Gmbh Process for producing polymeric films for use as fuel cells
US6444343B1 (en) 1996-11-18 2002-09-03 University Of Southern California Polymer electrolyte membranes for use in fuel cells
US5866353A (en) 1996-12-09 1999-02-02 Bayer Corporation Electro chemical biosensor containing diazacyanine mediator for co-enzyme regeneration
US5759712A (en) 1997-01-06 1998-06-02 Hockaday; Robert G. Surface replica fuel cell for micro fuel cell electrical power pack
US6306285B1 (en) 1997-04-08 2001-10-23 California Institute Of Technology Techniques for sensing methanol concentration in aqueous environments
US5904740A (en) 1997-06-03 1999-05-18 Motorola, Inc. Fuel for liquid feed fuel cells
GB9724022D0 (en) 1997-11-13 1998-01-14 Nat Power Plc Production of stretched ion exchange membranes
US6030718A (en) 1997-11-20 2000-02-29 Avista Corporation Proton exchange membrane fuel cell power system
US5919576A (en) 1997-11-21 1999-07-06 Health Research Inc. Immobilized biological membranes
US6087029A (en) 1998-01-06 2000-07-11 Aer Energy Resources, Inc. Water recovery using a bi-directional air exchanger for a metal-air battery
US6221523B1 (en) 1998-02-10 2001-04-24 California Institute Of Technology Direct deposit of catalyst on the membrane of direct feed fuel cells
US5992008A (en) 1998-02-10 1999-11-30 California Institute Of Technology Direct methanol feed fuel cell with reduced catalyst loading
US6146472A (en) 1998-05-28 2000-11-14 The Timken Company Method of making case-carburized steel components with improved core toughness
US6294281B1 (en) * 1998-06-17 2001-09-25 Therasense, Inc. Biological fuel cell and method
US6117577A (en) 1998-08-18 2000-09-12 Regents Of The University Of California Ambient pressure fuel cell system
CA2348789A1 (en) 1998-10-28 2000-05-04 The Regents Of The University Of California Fuel cell membrane humidification
WO2000036679A1 (en) 1998-12-18 2000-06-22 The Regents Of The University Of California Fuel cell anode configuration for co tolerance

Also Published As

Publication number Publication date Type
WO2000022688A3 (en) 2000-09-21 application
CN1336017A (en) 2002-02-13 application
US20030039868A1 (en) 2003-02-27 application
JP2002527874A (en) 2002-08-27 application
US6500571B2 (en) 2002-12-31 grant
US20020001739A1 (en) 2002-01-03 application
EP1110261A2 (en) 2001-06-27 application
CA2340980A1 (en) 2000-04-20 application
US20050158618A1 (en) 2005-07-21 application
WO2000022688A2 (en) 2000-04-20 application

Similar Documents

Publication Publication Date Title
Lewis Symposium on bioelectrochemistry of microorganisms. IV. Biochemical fuel cells.
Schröder Anodic electron transfer mechanisms in microbial fuel cells and their energy efficiency
Bond et al. Electricity production by Geobacter sulfurreducens attached to electrodes
Palmore et al. Electro-enzymatic reduction of dioxygen to water in the cathode compartment of a biofuel cell
Han et al. Direct methanol fuel-cell combined with a small back-up battery
Zhao et al. Application of pyrolysed iron (II) phthalocyanine and CoTMPP based oxygen reduction catalysts as cathode materials in microbial fuel cells
Kim et al. A mediator-less microbial fuel cell using a metal reducing bacterium, Shewanella putrefaciens
Sun et al. Improved performance of air-cathode single-chamber microbial fuel cell for wastewater treatment using microfiltration membranes and multiple sludge inoculation
Watanabe Recent developments in microbial fuel cell technologies for sustainable bioenergy
US5242764A (en) Near ambient, unhumidified solid polymer fuel cell
Cracknell et al. Enzymes as working or inspirational electrocatalysts for fuel cells and electrolysis
Zhang et al. Improved performances of E. coli-catalyzed microbial fuel cells with composite graphite/PTFE anodes
Behera et al. Performance of microbial fuel cell in response to change in sludge loading rate at different anodic feed pH
Freguia et al. Sequential anode–cathode configuration improves cathodic oxygen reduction and effluent quality of microbial fuel cells
Qian et al. A 1.5 µL microbial fuel cell for on-chip bioelectricity generation
Aelterman et al. The anode potential regulates bacterial activity in microbial fuel cells
Biffinger et al. A biofilm enhanced miniature microbial fuel cell using Shewanella oneidensis DSP10 and oxygen reduction cathodes
Osman et al. Recent progress and continuing challenges in bio-fuel cells. Part II: Microbial
Shukla et al. Biological fuel cells and their applications
US20020015871A1 (en) Electrochemical device and methods for energy conversion
Chae et al. Mass transport through a proton exchange membrane (Nafion) in microbial fuel cells
US20080286624A1 (en) Microbial fuel cells
US20040241528A1 (en) Implantable, miniaturized microbial fuel cell
US6495023B1 (en) Electrochemical methods for generation of a biological proton motive force and pyridine nucleotide cofactor regeneration
Kim et al. A miniature membrane-less biofuel cell operating under physiological conditions at 0.5 V

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

AK Designated states

Kind code of ref document: A3

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW

COP Corrected version of pamphlet

Free format text: PAGES 1/6-6/6, DRAWINGS, REPLACED BY NEW PAGES 1/5-5/5; DUE TO LATE TRANSMITTAL BY THE RECEIVING OFFICE

AL Designated countries for regional patents

Kind code of ref document: C2

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

AK Designated states

Kind code of ref document: C2

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW

WWE Wipo information: entry into national phase

Ref document number: 509839

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: 141393

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/001792

Country of ref document: MX

ENP Entry into the national phase in:

Ref document number: 2340980

Country of ref document: CA

Ref document number: 2340980

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020017002072

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2001/00498

Country of ref document: TR

WWE Wipo information: entry into national phase

Ref document number: 1999968444

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 25862/00

Country of ref document: AU

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1999968444

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020017002072

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 25862/00

Country of ref document: AU

WWR Wipo information: refused in national office

Ref document number: 1020017002072

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1999968444

Country of ref document: EP